Fixation of Dinitrogen to a Mesoscale Solid Salt Using a Titanium Oxide/Conducting Polymer System

Hoshino, Katsuyoshi; Inui, M.; Kitamura, Takashi; Kokado, Hiroshi

doi:10.1002/1521-3773(20000717)39:14<2509::aid-anie2509>3.0.co;2-i

Cited by 67 publications

(21 citation statements)

References 6 publications

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“…Relevant examples are reductive protonation to ammonia under concomitant oxidation of the central metal, oxidative alkylation with alkyl halogenides affording alkyldiazenido complexes, and successive addition of methyl lithium and trimethyloxonium tetrafluoroborate leading to a 1,2-dimethyldiazene complex. [16] These partly contradictory results induced contrary discussions, particularly by Edwards et al, and culminated in the conclusion that all the previously published values resulted from traces of the ubiquitous ammonia. In 1977 Schrauzer and Guth reported for the first time that the electron ± hole pairs generated by light absorption of a semiconductor powder reduce molecular nitrogen to ammonia.…”

Section: Introductionmentioning

confidence: 90%

Nitrogen Photofixation on Nanostructured Iron Titanate Films

Rusina

Linnik

Eremenko

et al. 2003

Chemistry A European J

107

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A nanostructured iron titanate thin film has been prepared by a sol-gel method from iron(III) chloride and titanium tetraisopropylate. Energy-dispersive X-ray analysis and Mössbauer spectroscopy suggest the presence of a Fe(2)Ti(2)O(7) phase, which was previously obtained as an intermediary phase upon heating ilmenite. In the presence of ethanol or humic acids and traces of oxygen, the novel film photocatalyzes the fixation of dinitrogen to ammonia (17 microM) and nitrate (45 microM). In the first observable reaction step, hydrazine is produced and then undergoes further photoreduction to ammonia. Oxidation of the latter by oxygen affords nitrate as the final product. Since the reaction occurs also in air and with visible light (lambda>455 nm), and since the iron titanate phase may be formed by the weathering of ilmenite minerals, it may be a model for mutual nonenzymatic nitrogen fixation in nature.

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Section: Introductionmentioning

confidence: 90%

Nitrogen Photofixation on Nanostructured Iron Titanate Films

Rusina

Linnik

Eremenko

et al. 2003

Chemistry A European J

107

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“…The photochemically induced cleavage of the N−N bond in a dimetalladinitrogen complex is a quite unique finding in this field and should provide new stimulus on how to achieve dinitrogen activation by the use of metals and light 11…”

Section: Methodsmentioning

confidence: 99%

Photochemical Activation of the N≡N Bond in a Dimolybdenum-Dinitrogen Complex: Formation of a Molybdenum Nitride

et al. 2001

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Herein we describe a novel contribution to the developing field of NN bond cleavage reactions, [1±3] in which we have for the first time cleaved the NN bond by using light and transition metal complexes. Only two groups [1, 2] have so far given detailed information on the pathways leading to the sixelectron reduction of dinitrogen. Such a reduction is a stepwise metal-assisted transformation consisting, usually, of a four-electron reduction of N 2 , leading to a dimetallahydrazone, L n MNÀNML n , followed by a final, thermally induced reductive cleavage of the residual NÀN bond. The present report focuses on the generation of the d 3 -[Mo(Mes) 3 ] frag-attraction between cationic ester 2 and vesicles rendered anionic by the presence of 1) likely augment hydrophobic association. Adjusted for the concentration differences, the intra-vesicular reaction rate is equivalent to that of the intermolecular reaction between monomeric species (Table 1, entry 2). An entropically favorable confinement of the reactants within the bilayer assembly must evidently compensate for any inhibitory rate effects inherent to the membrane environment.With all the control runs suitably investigated, we were able to examine the vesicle/vesicle reaction (Table 1, entry 7). Its t 1/2 of 4.2 min indicates a much faster reaction than vesicular 2 plus monomeric acetohydroxamate (Table 1, entry 4, t 1/2 180 min). This fact, plus the highly efficient intra-vesicular reaction evident in entry 6, suggests a reasonable mechanism for the vesicle/vesicle reaction: Collisions between vesicles containing l and vesicles containing 2 lead to a transfer of 2 from one vesicle population to the other. [18] (Potent steroidal anchoring of 1 has been shown previously to prevent a corresponding migration of the nucleophile within our timescale). [10] A fast intra-vesicular catalyzed hydrolysis, depicted schematically in Figure 1, ensues.A possible variation of the above vesicle-transfer mechanism was considered. Perhaps ester 2 departs from its vesicles, enters the water, and re-adsorbs into the vesicles containing nucleophile 1. To test this idea, we studied the vesicle/vesicle reaction with an ester in which the dodecyl chain had been replaced by an octadecyl group. Adding six more carbon atoms should seriously impede any partitioning of the ester from the membrane into the free solution.Yet the vesicle/vesicle rates with the octadecyl analogue are only fourfold smaller than with the dodecyl ester 2. This result is fully consistent with a collision-induced vesicle-to-vesicle transfer that is mildly retarded by the longer chain length. At the moment, organic reactivity among various colloidal particles is a scientific nursling. Further experimentation in the area, as colloid chemistry simulates and ultimately subsumes biology, is an easy call.

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“…They observed a correlation between NH 3 yield and the M-H bond strength, where a high-bond strength gives rise to a high NH 3 yield. Hoshino et al [129] reported N 2 photoreduction on needle-like solid ammonium perchlorate (NH 4 ClO 4 ) using a TiO 2 /conducting polymer (poly 3-methylthiophene, P3MeT) catalyst. Under illumination, photogenerated carriers at the TiO 2 /P3MeT interface contributed to NH 3 synthesis in the presence of water.…”

Section: Titania-based Photocatalystsmentioning

confidence: 99%

Alternative Strategies Toward Sustainable Ammonia Synthesis

Wang

Gong

2020

Trans. Tianjin Univ.

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As one of the world's most produced chemicals, ammonia (NH 3 ) is synthesized by Haber-Bosch process. This century-old industry nourishes billions of people and promotes social and economic development. In the meantime, 3%-5% of the world's natural gas and 1%-2% of the world's energy reserves are consumed, releasing millions of tons of carbon dioxide annually to the atmosphere. The urgency of replacing fossil fuels and mitigating climate change motivates us to progress toward more sustainable methods for N 2 reduction reaction based on clean energy. Herein, we overview the emerging advancement for sustainable N 2 fixation under mild conditions, which include electrochemical, photo-, plasma-enabled and homogeneous molecular NH 3 productions. We focus on NH 3 generation by electrocatalysts and photocatalysts. We clarify the features and progress of each kind of NH 3 synthesis process and provide promising strategies to further promote sustainable ammonia production and construct state-of-the-art catalytic systems.

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Fixation of Dinitrogen to a Mesoscale Solid Salt Using a Titanium Oxide/Conducting Polymer System

Cited by 67 publications

References 6 publications

Nitrogen Photofixation on Nanostructured Iron Titanate Films

Nitrogen Photofixation on Nanostructured Iron Titanate Films

Photochemical Activation of the N≡N Bond in a Dimolybdenum-Dinitrogen Complex: Formation of a Molybdenum Nitride

Alternative Strategies Toward Sustainable Ammonia Synthesis

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